CN101173146A - Aqueous coating composition based on a binder mixture as a base coat - Google Patents
Aqueous coating composition based on a binder mixture as a base coat Download PDFInfo
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- CN101173146A CN101173146A CNA2007101803572A CN200710180357A CN101173146A CN 101173146 A CN101173146 A CN 101173146A CN A2007101803572 A CNA2007101803572 A CN A2007101803572A CN 200710180357 A CN200710180357 A CN 200710180357A CN 101173146 A CN101173146 A CN 101173146A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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Abstract
The invention relates to aqueous coating compositions based on binder mixtures as base coats, to a process for their preparation, and to their use in single-coat or multicoat paint systems, in particular for coatings having chip-resistant properties. The aqueous coating composition comprises an aqueous binder mixture a) consisting of a1), a2) and A3), and B), wherein: A1)25 to 70 wt.% of a secondary hydroxyl-functional polyacrylate dispersion or polyacrylate emulsion, A2)5 to 50 wt.% of an aliphatic polyurethane dispersion, A3)20 to 70 wt.% of a hydroxyl-functional polyester-polyurethane dispersion, the polyester having a molecular weight of 500-2500 g/mol representing at least 75 wt.%, B) at least one crosslinking agent, the composition having to comprise at least two of the three components A1) to A3), having to comprise at least 35 wt.% of one component A1) and/or A3).
Description
The cross reference of related application
The application requires the right of priority of No. the 10 2,006 048 926.8, the German patent application submitted on October 17th, 2006 according to 35 U.S.C. § 119 (a)-(d).
Technical field
The present invention relates to water-based paint compositions based on the combination of aqueous binder and linking agent and preparation method thereof, and this coating composition is used for single coating or many layer of lacquer system, hits the coating of (anti-stonechip) character especially for having anti-stone.
Background of invention
In the automobile fine-processing technique, use the lacquer system of forming by priming paint, surfacer, undercoat and Clear coating usually.In this lacquer system in the different coating each all has many specific functions.
The description of existing in the prior art many productions about the single coating in this class laminated coating or this class laminated coating.
The effect of surfacer coating comprises the unevenness in the leveling car body, guarantees effectively to adhere with priming paint, by the elastic property by coating, guarantees falling the protection of infringement simultaneously, for example because the infringement that flag causes.This surfacer is divided into two-layer applying, and first coating is intended to the unevenness in the leveling car body, and second coating is used to produce anti-stone and hits character.But, in the prior art, the water-based surfacer system with single coating surfacer that satisfies above-mentioned two requirements has been described.
Undercoat, more particularly the metallicity undercoat is used to make coating system to have good film optical property, high glossiness and tangible metal effect, thereby guarantees through having attracting outward appearance on the product part of painting.
DE-A 195 42 626, DE-A 196 18 446 and DE-A 44 21 823 have also described water-based paint compositions, it comprises: as the binder blend of component (I), as the not end capped polyisocyanate crosslinker of component (II) and as the component (A1) of component (III) and/or (A2) and/or (A3) and/or aqueous dispersion (A4), described binder blend is made up of the acrylate copolymer in the organic solution (A1) and/or vibrin (A2) and/or urethane resin (A3).The system of describing in the literary composition can be used as finish paint, surfacer or automobile trimming lacquer.
WO-A 98/12001 has described the anti-stone with improvement and has hit the laminated coating of character, forms by the aqueous basecoat layer with based on the special powder Clear coating that can move to the polyacrylate resin in the undercoat.The shortcoming of this system be undercoat composition must with specific polyacrylic ester highly compatible.Character described in the literary composition only realizes by the combination of aqueous basecoat layer and special powder Clear coating and special curing, described curing is at first to make undercoat at 90 ℃ of preliminarily drieds, then undercoat and powder Clear coating is toasted together.
Still need suitable coating system to make the japanning operation more effective, and improve multilayer and coat with lacquer accurately machined property levels.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of binder combination, this combination will resist stone to hit the character of surfacer and the character of undercoat combines, therefore improved the quality of the 4-layer of lacquer system of forming by priming paint, surfacer, undercoat and Clear coating, perhaps even can save a coating in the 4-layer of lacquer system.The most critical that will meet requires to be not only reliable working properties in this article, and is that splendid undercoat tackiness, effective elasticity and anti-stone hits character, and the smooth character of leveling air spots effectively.Other target comprises good recoatability and trimming property, splendid film optical property, and for example levelling property, metal effect and DOI value (image difference), for example, best pigment wettability is for the height endurability of water, solvent and environment, light and climatic effects.Wish that equally binder combination of the present invention is enough stable when storing.
Be astoundingly, have been found that water-based paint compositions at present, said composition has at least two kinds, the combination of aqueous dispersion that preferred three kinds of chemical structures are different, wherein at least a, preferred two kinds have the crosslinked group of energy, and said composition comprises linking agent, has extraordinary anti-hitting property of stone.
The invention provides water-based paint compositions, it comprises by A1), A2) and the aqueous binder mixture A that A3) forms) and B), wherein:
A1) the secondary hydroxyl official of 25 weight % to 70 weight % energy polyacrylate dispersion or polyacrylate dispersion,
A2) the aliphatic urethane dispersion of 5 weight % to 50 weight %,
A3) the hydroxyl-functional polyester-polyurethane ester dispersion of 20 weight % to 70 weight %, molecular weight are that the polyester of 500-2500 gram/mole accounts for 75 weight % at least,
B) at least a linking agent,
Described composition must comprise A1) to A3) in three kinds of components at least two kinds, must the amount of comprising be at least a kind of component A1 of 35 weight %) and/or A3).
Embodiment
Unless indication is arranged in addition, specification sheets and claims comprise that all used among embodiment numerals think that all word " pact " modifies, even this speech does not conclusively show out.And any digital scope in the literary composition all should comprise all subranges that comprise in this scope.
The organic solvent content of coating composition of the present invention is 2 weight % to 12 weight %.
Can obtain the suitable second month in a season of (secondary) hydroxyl-functional polyacrylate dispersion A1 by following steps): with unsaturated compound (monomer) copolymerization in solvent, in and the bonded ionogenic group, be dispersed in the water.
Be applicable to the preparation secondary polyacrylate dispersion A1) monomeric example be the carboxyl-functional free radical polymerizable monomer, for example vinylformic acid, methacrylic acid, propenoic acid beta-carboxyl ethyl ester, Ba Dousuan, fumaric acid, toxilic acid (acid anhydride), methylene-succinic acid, the perhaps mono alkyl ester of diprotic acid and/or acid anhydrides, for example maleic acid mono alkyl ester.The acid of preferred use acrylic or methacrylic.
Suitable non-functional monomer is replaced in (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 4-tertiary butyl cyclohexyl, (methyl) vinylformic acid norborneol ester, (methyl) isobornyl acrylate, the alcohol moiety by alkyl on (methyl) cyclohexyl acrylate, the ring to have C
1-C
18(methyl) acrylate of alkyl, for example ethyl propenoate, Jia Jibingxisuanyizhi, n-butyl acrylate, n-BMA, isobutyl acrylate, Propenoic acid, 2-methyl, isobutyl ester, 2-EHA, methyl methacrylate, methacrylic acid 2-ethylhexyl, tert-butyl acrylate, vinylformic acid stearyl, methacrylic acid stearyl, vinylformic acid norborneol ester and/or methacrylic acid norborneol ester.
The example of suitable hydroxy functional monomers is to have C in the alcohol moiety
1-C
18The OH official of alkyl can (methyl) acrylate, for example hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester or methacrylic acid hydroxy butyl ester.
What be fit to equally is to contain the unitary carboxylic monomer of epoxy alkane, for example oxyethane, propylene oxide or butylene oxide ring and (methyl) acrylic acid adducts.Preferably hydroxyethyl methylacrylate and/or Rocryl 410.
Same what be fit to is vinylbenzene, Vinyl toluene, alpha-methyl styrene, vinyl ester, contain the unitary vinyl monomer of epoxy alkane, if the condensation product of (methyl) vinylformic acid and low polyalkylene oxide monoalky lether for example is and the suitable monomer that also contains the functional group of epoxy group(ing), alkoxysilyl, urea groups, carbamate groups, amide group or itrile group and so on.In monomeric gross weight is benchmark, and functionality can be 0 weight % to 3 weight % more than or equal to 2 vinyl monomer and/or (methyl) acrylate monomer as the consumption of two (methyl) vinylformic acid hexylene glycol ester.
Randomly, can also use other monomer.Suitable example comprises the unsaturated compound of the free redical polymerization with phosphoric acid ester and/or phosphonate group or sulfonic acid and/or sulfonate group.
Preferred monomer is methyl methacrylate, vinylbenzene, vinylformic acid, methacrylic acid, butyl acrylate, butyl methacrylate, tert-butyl acrylate, 2-EHA, methacrylic acid 2-ethylhexyl, hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester or methacrylic acid hydroxy butyl ester.
At secondary polyacrylate dispersion A) in, the monomeric amount of carboxyl-functional is 0.8 weight % to 5 weight %, is preferably 1.2 weight % to 4 weight %, the amount of hydroxy functional monomers is 1 weight % to 45 weight %, is preferably 6 weight % to 30 weight %.
Suitable polymerization starter is a peralcohol, for example diacyl peroxide, alkyl super-acid ester, dialkyl peroxide, peroxy dicarbonate, inorganic peroxide or azo-compound.
In principle, all organic solvents all are applicable to the preparation polyacrylic ester.Solvent can any needs amount use, preferable amount is less than 20 weight % (is benchmark in monomeric gross weight), so that the solvent in the dispersion is lower.The solvent mixture that preferably comprises hydrophobic solvent and hydrophilic solvent, described hydrophobic solvent is solvent naphtha, toluene, dimethylbenzene, Kristalloel for example, and described hydrophilic solvent is butyleneglycol, butyldiglycol, glycol ether, propylene glycol monomethyl ether or dipropylene glycol monomethyl ether for example.
In principle, can prepare secondary polyacrylate dispersion, for example tailing method (feed processes) and batch of material method (batch processes), perhaps cascade method (cascade processes) by any method of prior art.
Preferred secondary hydroxyl official can polyacrylate dispersion A1) can obtain by following steps: make a) and b) mixture reaction:
A) has C in the alcohol moiety of 30 weight % to 85 weight %
1-C
18(methyl) acrylate and/or the vinyl aromatic compounds of aliphatic hydrocarbyl,
B) hydroxyl-functional (methyl) acrylate of 5 weight % to 35 weight %,
Reaction obtains hydrophobic polymer, is adding a) and b then) afterwards, be metered into c), d) and mixture e):
C) has C in the alcohol moiety of 4 weight % to 20 weight %
1-C
18(methyl) acrylate and/or the vinyl aromatic compounds of aliphatic hydrocarbyl,
D) hydroxyl-functional (methyl) acrylate of 4 weight % to 15 weight % and
E) acid functional monomer of 1 weight % to 5 weight %, for example acrylic or methacrylic acid,
Polymerization obtains hydrophilic polymer, add a), b), c), d) and e) in, be metered into the initiator of 0.5 weight % to 6.5 weight %, a), b), c), d) and percentage ratio sum e) be 100 weight %.
As solvent, preferably use the mixture of hydrophilic solvent such as butyleneglycol and hydrophobic solvent such as solvent naphtha.
After polyreaction finishes, polymers soln is dispersed in the water, perhaps add entry and disperse.Can be before disperseing or simultaneously at dispersive, add the amine of the usefulness that neutralize with disperse water, perhaps add the amine of the usefulness that neutralizes with disperse water parallelly, usefulness amine and/or alkali neutralizing acid group, thus make acid groups be converted into the salt group.The neutral degree can be between 50% to 150%, preferably between 60% to 120%.
After disperseing, can remove part or all solvent for use by distillation.
The amine of preferred neutralization usefulness is dimethylethanolamine, ethyl diisopropyl amine, methyldiethanolamine and 2-aminomethyl-2-methylpropanol.
The pH value of secondary polyacrylate dispersion is 5-11, is preferably 6-10.Solids content is 20 weight % to 60 weight %, is preferably 35 weight % to 55 weight %.The mean particle size of dispersion is the 20-400 nanometer.
In the secondary polyacrylate dispersion of preparation, can also use so-called reactive thinner replace solvents, perhaps use with solvent.Suitable reactive thinner is for example: at room temperature be 2 and/or 3 polyethers for the functionality of liquid; Low-viscosity polyester, for example 1 moles of dicarboxylic acids (for example dimer (fatty acid) yl or hexanodioic acid) and 2 moles of glycol or triol or 2 moles of Cardura
The reaction product of E10 (glycidyl ester of Versatic acid, HexionSpecialities USA).What be suitable as reactive thinner equally is the reaction product of caprolactone and low-molecular-weight alcohol.What be fit to equally is Viscotrol C and other hydroxyl-functional oil.
Suitable hydroxyl-functional polyacrylate dispersion A1) be by known copolymerization process, in water-based emulsion, those hydroxyl-functional polyacrylate dispersions of preparation in the presence of suitable tensio-active agent.For example, at R.O.Athey jr., Emulsion Polymer Technology, Dekker, New York has described polyacrylate dispersion and preparation method thereof in 1991.
In principle, be equally applicable to prepare polyacrylate dispersion about preparing the monomer of pointing out in the secondary polyacrylate dispersion.
In this article, initiator can be included in the initial charge and/or add concurrently, comprises, if suitable, they are with charging in advance or time-delay charging (delayed feed) and/or increase charging (extended feed) adding.The example of suitable initiator comprises redox system, superoxide, persulphate and/or azo-compound, for example dibenzoyl peroxide, peroxidation two cumenes, cumene hydroperoxide, potassium peroxydisulfate, peroxo disulfate acid ammonium, Diisopropyl azodicarboxylate or di-t-butyl peroxide.The redox initiator that adds can be iron (II) ion for example.
Preferred polyacrylate dispersion A) by in water, in the presence of initiator and tensio-active agent, to a), b), c) and d) carry out letex polymerization and obtain, wherein:
A) hydroxyl-functional (methyl) acrylate of 10 weight % to 40 weight %,
B) has aliphatic C in the alcohol moiety of 40 weight % to 90 weight %
1-C
18(methyl) acrylate and/or the vinyl aromatic compounds of alkyl,
C) acid functional monomer of 0 weight % to 5 weight %, for example acrylic or methacrylic acid,
D) other monomer of 0 weight % to 25 weight %, for example vinyl cyanide, vinyl-acetic ester and vinyl pyrrolidone.
Also be suitable as component A1) be the mixed form of polyacrylic acid dispersion, for example polyester-polyacrylate dispersions.These dispersions contain polyacrylic ester segment and polyester segment simultaneously, by for example in the presence of polyester, make and are carrying out free radical (being total to) polyreaction and make about preparing the monomer described in the secondary polyacrylate dispersion.
This reaction is carried out mutually with body, perhaps preferably carries out in organic solution.Polyester acrylate contains the polyester portion of 10 weight % to 75 weight %, preferred 20 weight % to 60 weight %.
Preferred hydroxyl-functional polyester-polyacrylate dispersions by by a), b) and the mixture c) formed at d) in the presence of carry out the free radical initiation polyreaction make, wherein:
A) has aliphatic C in the alcohol moiety of 20 weight % to 70 weight %
1-C
18(methyl) acrylate and/or the vinyl aromatic compounds of alkyl,
B) hydroxyl-functional (methyl) acrylate of 3 weight % to 35 weight %,
C) acid functional monomer of 2 weight % to 8 weight %, for example acrylic or methacrylic acid,
D) the hydroxyl-functional polyester of 75 weight % to 10 weight %, if suitable, this polyester is by having the group that can carry out graft polymerization in conjunction with double bond containing component.
Preferred initiator is di-t-butyl peroxide and crosses the sad tert-butyl ester.The consumption of initiator is 0.5 weight % to 5 weight %.Be reflected under 90 ℃ to 180 ℃ the temperature and carry out.
Institute's bonded acid groups partially or completely with the amine reaction of neutralization usefulness, preferred amine is dimethylethanolamine, ethyl diisopropyl amine or 2-aminomethyl-2-methylpropanol.Be dispersed in then in the water, perhaps water disperses.
Suitable polyurethane dispersions A2) is the conventional polyurethanes or the polyurethane/polyurea of the common self-emulsifying of aqueous form.
Urethane is self-emulsifying by coupled ion type and/or non-ionic hydrophilic group in polymer chain.Hydrophilic radical bonded mode has many, for example, hydrophilic radical directly can be attached in the polymer chain, and they are connected as side chain or end group.
Suitable polyurethane dispersions can prepare in melt or organic solution by method known to those skilled in the art, disperses then; If suitable,, can in dispersion steps or after dispersion steps, in organic solution, carry out the so-called chain reaction that increases in order to improve molecular weight.
Usually use following raw material, they react to each other, to prepare suitable polyurethane dispersions A):
1) at least a NCO-activity unit that is used for hydrophilic radical is attached to urethane, hydroxycarboxylic acid for example, example is a dihydroxymethyl acetate, 2, the 2-dimethylol propionic acid, 2, the 2-acid dimethyl, 2,2-dihydroxymethyl valeric acid, dyhydrobutanedioic acid, the mixture of hydroxy new pentane acid or this class acid, hydroxyl sulfoacid, aminocarboxylic acid, for example isophorone diamine or quadrol and acrylic acid Michael-adduct, thionamic acid, for example aminoethyl ethyl sulfonic acid, for example hydroxyl or amino-functional phosphonic acids and/or molecular weight are the simple function of 350-2500 gram/mole, two senses or trifunctional polyethylene oxide unit can also use the mixture of different hydrophilic type reagent.Component 1) consumption should be able to obtain the stabilized aqueous dispersion.
The NCO-activity unit that is particularly suitable in conjunction with hydrophilic radical is a dimethylol propionic acid, and dimethylolpropionic acid, molecular weight are monohydroxy or the dihydroxyl official energy polyethylene oxide unit of 350-2500, and for example Polyether LB 25
(based on the monohydroxy functional polyethers of oxyethane, Bayer MaterialScience AG, DE), Carbowax
750 (based on the monohydroxy functional polyethers of oxyethane, Dow Chemicals, USA), Pluriol
A 500 (based on the monohydroxy polyethers of oxyethane, BASF AG, Ludwigshafen, Germany), and hydroxyl or amino-functional sulfonic acid and/or sulphonate.
2) at least a aliphatic series and/or aromatic diisocyanate or polyisocyanates, example is that functionality is 2 or 3 aliphatic isocyanate, for example 1, hexamethylene-diisocyanate, butane vulcabond, isophorone diisocyanate, 1-methyl-2,4 (2,6)-two isocyanato hexanaphthene, norbornene alkyl diisocyanate, eylylene diisocyanate, tetramethyl-eylylene diisocyanate, six hydrogen eylylene diisocyanates, nonane vulcabond and 4,4 '-two isocyanato dicyclohexyl methyl hydrides.It is same that what be fit to is to follow the use aromatic isocyanate, for example 2,4 (2,6)-two isocyanato toluene or 4,4 '-two isocyanato phenylmethanes, and molecular weight is high molecular or the oligomeric polyisocyanates based on above-mentioned aliphatic isocyanate of 336-1500.Preferred 4,4 '-two isocyanato dicyclohexyl methyl hydrides and/or isophorone diisocyanate and/or hexamethylene diisocyanate and/or 1-methyl-2,4 (2,6)-two isocyanato hexanaphthene of using.Especially preferably use isophorone diisocyanate and/or hexamethylene diisocyanate, perhaps the mixture of 4,4 '-two isocyanato dicyclohexyl methyl hydrides and isophorone diisocyanate or hexamethylene diisocyanate.
3) at least a molecular weight is the polyol component based on polyester, polyesteramide, polyacetal, polyethers and/or polysiloxane and/or polycarbonate of 500-18000 gram/mole, and its functionality is 1-5, is preferably 2-2.5.
Be applicable to preparation polyurethane dispersions A) polyol component 3) can comprise following:
Average functionality is the polyester polyol of 1.5-5.Specially suitable is other polyester polyol of straight chain polyester glycol or reduced branching degree, for example by known method by aliphatic series, the polyester polyol of alicyclic or aromatic dicarboxylic acid and/or poly carboxylic acid and/or their acid anhydrides and polyvalent alcohol preparation, described carboxylic acid is Succinic Acid for example, pentanedioic acid, toxilic acid, fumaric acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, the nonane dicarboxylic acid, decane dicarboxylic acid, dimer (fatty acid) yl, terephthalic acid, m-phthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or trihemellitic acid, or their mixture, perhaps described acid and other dicarboxylic acid and/or polycarboxylic mixture, described polyvalent alcohol is ethylene glycol for example, glycol ether, triglycol, Tetraglycol 99,1, the 2-propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol, 1, ammediol, butane-1, the 4-glycol, butane-1, the 3-glycol, butane-2, the 3-glycol, pentane-1, the 5-glycol, hexane-1, the 6-glycol, 2,2-dimethyl-1, ammediol, 1,4-dihydroxyl hexanaphthene, 1, the 4-hydroxymethyl-cyclohexane, octane-1, the 8-glycol, decane-1, the 10-glycol, dodecane-1,12-glycol or their mixture, if it is suitable, can also follow the polyvalent alcohol that uses high functionality, for example TriMethylolPropane(TMP) or glycerol.What be suitable as equally that polyvalent alcohol prepares polyester polyol is alicyclic and/or aromatic dihydroxy and polyol.Can also use corresponding multi-carboxy anhydride or corresponding polycarboxylic low-carbon-ester or their mixture to replace the free poly carboxylic acid to prepare polyester.
Can also follow the use monofunctional carboxylic pro rata, for example phenylformic acid, thylhexoic acid, soy(a)-bean oil fatty acid, peanut oil fatty acid, oleic acid, saturated C
12-C
20Lipid acid and/or their mixture can also use hexalin, isooctyl alcohol and Fatty Alcohol(C12-C14 and C12-C18).
Polyester polyol can certainly be the homopolymer or the multipolymer of lactone, preferably by lactone or interior ester mixture and suitable functionality be 2 and/or the addition reaction of higher starting molecule obtain, described lactone is butyrolactone, 6-caprolactone and/or methyl-6-caprolactone for example, for example above-mentioned low molecular weight polyols as the synthetic component of polyester polyol of described starting molecule.Particularly preferably be the polymkeric substance of corresponding 6-caprolactone.
The polycarbonate that contains hydroxyl also is suitable as polyhydroxy component, and example is can be by glycol as 1,4-butyleneglycol and/or 1, the polycarbonate of 6-hexylene glycol and/or pentanediol and diaryl carbonate such as diphenyl carbonate or phosgene reaction preparation.
The example of the polyether glycol that can mention is the polyadduct of Styrene oxide 98min., oxyethane, propylene oxide, tetrahydrofuran (THF), butylene oxide ring, Epicholorohydrin, their common adducts and graft product, and polyether glycol that obtains by polyol condensating or their mixture, and the polyether glycol that obtains of the alkoxylate by polyfunctional alcohol, amine and amino alcohol.
Also can use segmented copolymer, for example polyether-polyester or polycarbonate-polyester or polycarbonate polyethers based on above-mentioned polyvalent alcohol.
Preferred polyester polyol and/or polycarbonate polyol and/or the C of using
3And/or C
4Polyether glycol.Especially preferably use combination or the polycarbonate polyol and the C of the pure and mild polycarbonate polyol of polyester polyols
4The combination of polyether glycol.
4) if suitable, lower molecular weight (molecular weight＜500 gram/moles) glycol, triol or tetrol, for example 1,4-butyleneglycol, 1,6-hexylene glycol, ethylene glycol, TriMethylolPropane(TMP), neopentyl glycol, glycerol, tetramethylolmethane and/or amino alcohol, for example if diethanolamine, thanomin, diisopropanolamine (DIPA) or Propanolamine suitable, comprise ethoxylation and/or propoxylation form.
5) if suitable, the material that is called chain extension agent is diamines and/or polyamines and/or amino alcohol for example, diethanolamine for example, 1, the 2-diaminopropanes, 1, the 4-diaminobutane, 2,5-diamino-2,5-dimethylhexane, 1,5-diamino-2-methylpentane (Dytek A, DuPont), 1,2,2,4-and/or 2,4,4-trimethylammonium-1,1,11-diamino undecane, 1,12-diamino dodecane or triaminononane, quadrol, isophorone diamine, diethylenetriamine, hydrazine, adipic dihydrazide, hydroxy-ethylenediamine, the dihydroxy ethyl quadrol, aminopropanol, aminoalkoxy silane and their mixture.Can also be by making from 1), 2), 3) and 4) the NCO group of prepolymer and water section or reaction fully increase chain.
Preferred polyurethane dispersions A2) comprise following material as synthetic component:
1) at least a NCO-activity unit that contains at least one hydrophilic radical of 0.5 weight % to 10 weight %,
2) aliphatic series and/or alicyclic diisocyanate or the polyisocyanates of 8 weight % to 60 weight %,
3) at least a molecular weight of 20 weight % to 90 weight % is that 500-18000 gram/mole, average functionality are the polyol component of 2-3,
4) low molecular weight diols and/or the triol of 0 weight % to 8 weight %,
5) diamines of 0 weight % to 6 weight % and/or hydrazine and/or hydrazides and/or amino alcohol and/or water are as chain extension agent.
Particularly preferred polyurethane dispersions A2) comprise as the following material that synthesizes component:
1) at least a NCO-activity unit that contains at least one carboxyl and/or carboxylic acid ester groups and/or sulfonate group of 1.4 weight % to 6.5 weight %, if suitable, can with molecular weight the polyethylene oxide unit combination of 350-2500 gram/mole,
2) aliphatic series and/or the alicyclic diisocyanate of 15 weight % to 50 weight %,
3) at least a molecular weight of 40 weight % to 83 weight % be 800-2400 gram/mole based on polyester and/or polycarbonate and/or C
3And/or C
4The polyol component of ether,
4) low molecular weight diols and/or the triol of 0 weight % to 4 weight %, for example hexylene glycol, butyleneglycol, ethylene glycol, glycerol, TriMethylolPropane(TMP), and the reaction product of they and 1-6 moles of ethylene oxide and/or propylene oxide,
5) diamines of 0 weight % to 4 weight % and/or hydrazine and/or hydrazides and/or amino alcohol and/or water is as chain extension agent,
Be used for and the content of carboxyl and/or sulfonic reagent is the 50-150 equivalent.
Usually, in melt or organic solution, prepare in the process of polyurethane dispersions, unit 1), 2), 3) and (if suitable) 4) reaction forms the isocyanate-functional prepolymer, this reaction can be undertaken by a reactions steps or (if suitable) two or more successive reactions steps.The isocyanate-functional prepolymer subsequently in melt, in organic solution or in aqueous dispersion with chain extension agent 5) reaction, form the high molecular water-dispersion or the dispersible urethane of water.If suitable, remove used solvent whole or in part by distillation subsequently.The suitable neutral amine that is used for is for example about preparing the amine described in the secondary polyacrylate dispersion, after increasing the reaction of chain reaction and isocyanate groups, could add isocyanic ester is had active neutralization reagent.Suitable solvent is acetone or methylethylketone, N-Methyl pyrrolidone or the N-ethyl pyrrolidone of often removing by distillation.
Described reaction can also use catalyzer common in the polyurethane chemistry field to carry out, and for example dibutyl tin laurate, dibutyltin oxide, two stannous octoates, tin chloride and tertiary amine are to accelerate speed of reaction and/or to obtain specific effect.
Polyurethane dispersions A2 in the binder combination of the present invention) solids content is generally 25 weight % to 60 weight %, and the pH value is 5.5-11, and mean particle size is the 20-500 nanometer.
Suitable hydroxyl-functional polyester-polyurethane ester dispersion A3) be 1), 2), 3) and 4) reaction product, wherein:
1) dimethylol propionic acid and/or the hydroxy new pentane acid of 2 weight % to 7 weight %, preferred 2 weight % to 5 weight %, if it is suitable, be used in combination with simple function, two sense polyethylene oxide unit (as preferably based on the monohydroxy functional polyethers of oxyethane or methoxy poly (ethylene glycol))
2) 7 weight % to 30 weight %, preferred 8 weight % to 22 weight %'s comprises 1, hexamethylene-diisocyanate and/or two (4-isocyanato hexanaphthene) methane and/or 1-methyl-2,4 (2,6)-two isocyanato hexanaphthene and/or 1-isocyanato-3,3, the mixture of 5-trimethylammonium-5-isocyanatomethyl hexanaphthene
3) molecular weight of 60 weight % to 91 weight %, preferred 70 weight % to 88 weight % is the polyol component based on polyester, polyesteramide, polyacetal, polyethers, polysiloxane and/or polycarbonate of 500-8000 gram/mole, its functionality is 1.8-5, be preferably 2-4, wherein 50 weight %, preferred 75 weight %, more preferably the polyol component of 100 weight % is made up of at least a polyester
4) lower molecular weight of 0 weight % to 5 weight % (molecular weight＜500 gram/moles) glycol, triol, tetrol and/or amino alcohol.
Described component is reacted in organic solution or melt, if it is suitable, use catalyzer common in the polyurethane chemistry and/or in the presence of as the nonactive amine of neutralizing agent such as triethylamine, ethyl diisopropyl amine and N-methylmorpholine, react, obtain the hydroxyl-functional polyester-polyurethane, in component 1), 2), 3) and 4) reaction after, no longer contain any free isocyanate group.
Then, disperse in water or water disperses, if suitable, excessive solvent is removed in distillation.
Can be for example diethanolamine, dimethylethanolamine, methyldiethanolamine, ammoniacal liquor or about preparing the neutralizing agent described in the secondary polyacrylate dispersion at the suitable neutralizing agent that adds before the dispersion steps or in the process in dispersion steps.
Polyester-polyurethane ester dispersion A3) solids content is 25 weight % to 55 weight %, and the pH value is 6-11, and mean particle size is the 10-350 nanometer.
B component) comprises cross-linking agent resin, acid amides-and amine-formaldehyde resin, resol, air aldehyde resin and ketone resin for example is such as phenol-formaldehyde resin, soluble phenolic resin, furane resin, urea resin, carbamate resins, cyanate resin, melamine resin, benzo guanamine resin, cyanamide resin, aniline resin, water-dilutable and water dispersible melamine-and melocol condensation product.
Same fit closely cross-linking agent resin B) is based on following listed blocked polyisocyanates: 1, hexamethylene-diisocyanate, two (4-isocyanato hexanaphthene) methane, 1, the 3-phenylene diisocyanate, 1,4-fourth vulcabond, the methyl pentamethylene diisocyanate, 1,12-dodecane vulcabond, 1, the 4-cyclohexyl diisocyanate, 1-isocyanato-3,3,5-trimethylammonium-5-isocyanatomethyl hexanaphthene, 4,4 '-two isocyanato dicyclohexyl methyl hydrides, 2,2-two (4-isocyanato cyclohexyl) propane, 1, the 4-phenylene diisocyanate, 1-methyl-2,4 (2,6) isocyanato hexanaphthene-two, 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 4,4 '-two isocyanato phenylmethanes, 2,2 '-and 2, the 4-diphenylmethanediisocyanate, to eylylene diisocyanate, right-different phenylene vulcabond, 4-isocyanatomethyl-1,8-octane vulcabond, to eylylene diisocyanate and α, α, α ', α '-tetramethyl---or-right-eylylene diisocyanate and their mixture.
As what recognized, on the polyisocyanates basis that is exemplified, can also use in the polyurethane chemistry field known have more high functionality and contain uretdion and/or the polyisocyanates of carbodiimide and/or allophanate group and/or isocyanuric acid ester group and/or carbamate groups and/or iminooxadiazinedione base and/or diazine three ketone groups and/or biuret groups as end capped cross-linking agent resin.
Can also use the mixture of different vulcabond and/or polyisocyanates.
The end-capping reagent that is applicable to polyisocyanate crosslinker is as follows: single alcohol, for example methyl alcohol, ethanol, butanols, hexanol and phenylcarbinol; Oxime, for example acetoxime and methyl ethyl ketoxime; Lactan, for example hexanolactam; Phenol; CH-acidic cpd, for example acetylacetic ester, perhaps malonic ester, for example diethyl malonate; Dimethyl pyrazole; Amine, for example tert-butyl benzyl amine, triazole, triazol-dimethyl, dicyclohexyl amine or Diisopropylamine.
The preferred amino crosslinker resin that uses, preferably same and blocked polyisocyanates is used in combination.
In yet another embodiment of the present invention, water-based paint compositions of the present invention comprises:
C) one or more are selected from polyurethane dispersions C1), polyacrylate dispersion C2) or polyurethane-polyacrylate dispersion C3) dispersion.
The preferred adhesive combined feature be to use in the time that is being less than 30 minutes 20 ℃ temperature and under up to 75% atmospheric moisture can physical dryness dispersion as component C).Particularly preferably be the functional polyurethane dispersions C1 of non-hydroxyl), C1) with A2) identical.Preferably with A2) described in aliphatic polyisocyanate serve as basis preparation polyurethane dispersions.Can also use described dispersion C1), C2) and mixture C) as component C).
If after dispersion is drop-down (drawing-down) film forming, stay noncohesive film after the volatile constituent volatilization, then think this dispersion physical dryness at room temperature.Among the present invention preferably with at room temperature less than 1 hour, be more preferably less than in time of 30 minutes can physical dryness dispersion as dispersion C).
Suitable polyacrylate dispersion C2) be at A1) in those polyacrylate dispersions of describing.
Polyurethane-polyacrylate dispersion C3) can be by in the presence of polyurethane dispersions for example, the emulsion polymerization that (methyl) acrylate, (methyl) vinylformic acid, (methyl) hydroxyalkyl acrylate, vinylbenzene and (if desired) other monomer carry out the free radical initiation makes.In this polymerization process, may there be the reaction that is grafted on the urethane.Can also carry out specific graft reaction in the urethane by unsaturated compound is attached to, and the copolyreaction between urethane and the polyacrylic ester.Can also in the presence of the unsaturated monomer of vinylbenzene, butyl acrylate and/or methyl methacrylate and so on, after scatter operation, carry out monomeric polyreaction and prepare urethane.
Particularly preferred polyurethane dispersions C1) comprise the reaction product of following material:
1) dimethylol propionic acid of 1.4 weight % to 6.5 weight %, if suitable, with molecular weight be that the polyethylene oxide unit combination of 750-2500 gram/mole is used,
2) hexamethylene diisocyanate of 15 weight % to 35 weight % and/or isophorone diisocyanate and/or two (4-isocyanato hexanaphthene) methane and/or 1-methyl-2,4 (2,6)-two isocyanato hexanaphthene,
3) at least a molecular weight of 45 weight % to 80 weight % be 840-2400 based on polyester and/or polycarbonate and/or C
3Or C
4The polyol component of ether,
4) hexylene glycol, butyleneglycol, neopentyl glycol, glycerol and/or the TriMethylolPropane(TMP) of 0 weight % to 3 weight %,
5) diamines of 0 weight % to 2.5 weight % and/or amino alcohol and/or water is as chain extension agent,
In carboxyl and sulfonic amount is benchmark, and the amount of the neutralizing agent that comprises is the 50-125 equivalent, does not have any organic solvent.
Coating composition of the present invention comprises:
A) the aqueous binder mixture of 15 weight % to 90 weight %, preferred 25 weight % to 85 weight %,
B) at least a linking agent of 5 weight % to 40 weight %, preferred 9 weight % to 32 weight %,
C) one or more of 5 weight % to 65 weight %, preferred 20 weight % to 55 weight % are selected from polyurethane dispersions C1), polyacrylate dispersion C2) or polyurethane-polyacrylate dispersion C3) dispersion,
A), percentage ratio sum C B)) is 100 weight %.
Equally, an embodiment of the invention are the water-based paint compositions of the present invention that comprise following component:
C) one or more are selected from polyurethane dispersions C1), polyacrylate dispersion C2) or polyurethane-polyacrylate dispersion C3) dispersion,
D) water-dilutable hydroxyl-functional vibrin.
Another embodiment of the invention is the water-based paint compositions of the present invention that comprises following component:
D) water-dilutable hydroxyl-functional vibrin.
Be suitable as component D) the water-dilutable polyester be dispersion resin with very good pigment wettability or pigment affinity.Component D) acid number is a 25-75 milligram KOH/ gram solid, and/or hydroxy radical content is 2.5 weight % to 10 weight %, and/or molecular weight is 750-5000 gram/mole, and/or the content of fatty acid component is 15 weight % to 50 weight %.
Preferred dispersion resin D) be by making 1), 2), 3) reaction, polyester and 4 then) the water-dilutable polyester of prepared in reaction:
1) glycol of selecting oneself, neopentyl glycol, glycol ether, ethylene glycol, the propane-1 of 30 weight % to 62 weight %, 2-glycol, propane-1, the glycol of 3-glycol and/or 1-butyleneglycol
2) triol that is selected from TriMethylolPropane(TMP), glycerol and/or tetramethylolmethane and/or the tetrol of 5 weight % to 20 weight %
3) dicarboxylic acid that is selected from Tetra hydro Phthalic anhydride, m-phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid and/or hexanodioic acid of 30 weight % to 62 weight %,
4) acid anhydrides of 3 weight % to 15 weight % (preferred trihemellitic acid acid anhydride),
Above-mentioned percentage ratio sum is 100 weight %, partly or entirely acid groups by be used for the reaction of neutral amine and be converted into salt form.
Coating composition of the present invention comprises:
A) the aqueous binder mixture of 15 weight % to 89.5 weight %, preferred 25 weight % to 85 weight %,
B) at least a linking agent of 5 weight % to 40 weight %, preferred 10 weight % to 30 weight %,
C) one or more of 5 weight % to 65 weight %, preferred 20 weight % to 50 weight % are selected from polyurethane dispersions C1), polyacrylate dispersion C2) or polyurethane-polyacrylate dispersion C3) dispersion,
D) the water-dilutable hydroxyl-functional vibrin of 0.5 weight % to 30 weight %, preferred 0.5 weight % to 15 weight %,
A), C B)) and percentage ratio sum D) be 100 weight %.
In another embodiment, coating composition of the present invention can comprise:
A) the aqueous binder mixture of 30 weight % to 94.5 weight %, preferred 55 weight % to 90 weight %,
B) at least a linking agent of 5 weight % to 40 weight %, preferred 10 weight % to 30 weight %,
D) the water-dilutable hydroxyl-functional vibrin of 0.5 weight % to 30 weight %, preferred 0.5 weight % to 15 weight %,
A), B) and percentage ratio sum D) be 100 weight %.
Suitable polyester dispersions and solution D) make by following steps: make the hydroxyl-functional polyester (by functionality be 1,2 and/or higher alcohol and carboxylic acid and/or its anhydride reaction elimination of water make) react by this way at 60-200 ℃, preferred 120-180 ℃ with the acid anhydrides of Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, maleic anhydride, trihemellitic acid acid anhydride and PMA and so on: the hydroxyl reaction of acid anhydrides and a part, follow the open loop of acid anhydrides simultaneously, be attached in the polyester.Obtain hydroxyl-functional and carboxyl-functional polyester like this, in partially or completely and behind the carboxyl, can be dispersed or dissolved in the water.The mean particle size of waterborne polyester solution is the 10-200 nanometer, is preferably the 25-100 nanometer.
The example that is applicable to the raw material of preparation hydroxyl-functional polyester is a glycol, for example ethylene glycol, butyleneglycol, glycol ether, triglycol, polyalkylene glycol such as polyoxyethylene glycol, propylene glycol, butane-1,4-glycol, hexane-1,6-glycol, neopentyl glycol or hydroxy new pentane acid DOPCP, preferably last three kinds.If suitable, the example of operable polyvalent alcohol comprises TriMethylolPropane(TMP), glycerol, tetrahydroxybutane, tetramethylolmethane, trishydroxymethyl benzene or tris(2-hydroxy ethyl)isocyanurate.Suitable dicarboxylic acid and polycarboxylic example comprise following: phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane dicarboxylic acid, hexanodioic acid, nonane diacid, sebacic acid, pentanedioic acid, tetrachlorophthalic acid, toxilic acid, fumaric acid, methylene-succinic acid, propanedioic acid, suberic acid, 2-pyrovinic acid, 3,3-diethyl glutarate, 2,2 ,-dimethyl succinic acid, trihemellitic acid or pyromellitic acid.If these sour acid anhydrides exist, equally also can use.Therefore, for the present invention, acid anhydrides is included in the definition of " acid ".In addition, also can use monocarboxylic acid.Suitable monocarboxylic acid is fatty acid distribution of coconut oil, soy(a)-bean oil fatty acid, Thistle oil lipid acid, castor-oil plant lipid acid, ricinine acid (ricinene acid), peanut oil fatty acid, ready denier oil acid or conjugated fatty acids (conjuene fattyacid), phenylformic acid, p t butylbenzoic acid, hexahydrobenzene formic acid, 2 ethyl hexanoic acid, different n-nonanoic acid, capric acid or octadecanoic acid.
In addition, when the preparation polyester, can also use 6-caprolactone.
Polycondensation by described raw material prepares the hydroxyl-functional polyester, if suitable, uses suitable esterifying catalyst, then with anhydride reaction.The polyester of preparation like this is dissolved in solvent or the solvent mixture, mixes with neutralizing agent.
Be dispersed or dissolved in the water step can polyester manufacture and with anhydride reaction after directly carry out, perhaps carry out after a while.
A kind of polyester dispersions or polyester liquid D of preferably being used for) polymer blend can obtain by following material is synthetic:
A) glycol of 30 weight % to 62 weight %, preferred 30 weight % to 50 weight %, its glycol of selecting oneself, butyleneglycol, ethylene glycol, glycol ether and/or neopentyl glycol,
B) triol and/or the tetrol of 5 weight % to 20 weight %, preferred 6 weight % to 15 weight %, preferably TriMethylolPropane(TMP) and/or glycerol,
C) dicarboxylic acid and/or its acid anhydrides of 30 weight % to 62 weight %, preferred 33 weight % to 58 weight %, it is selected from Tetra hydro Phthalic anhydride, m-phthalic acid, tetrahydrophthalic acid, terephthalic acid and/or hexanodioic acid,
D) monocarboxylic acid and/or the caprolactone of 0 weight % to 30 weight %, preferred 0 weight % to 20 weight %,
E) acid anhydrides of 3 weight % to 15 weight %, preferred 5 weight % to 12 weight %, it is selected from trihemellitic acid acid anhydride, Tetra Hydro Phthalic Anhydride and/or Tetra hydro Phthalic anhydride.
Polyurethane dispersions A2)/C1) the number-average molecular weight M that determines by gel chromatography
nUsually＞10000 gram/mole is preferred＞30000 gram/moles.Polyurethane dispersions contains a certain proportion of ultra high molecular weight part usually, and they can not be dissolved in the organic solvent fully, thereby has avoided molecular weight determination.
Polyester-polyurethane ester dispersion A3) the number-average molecular weight M that determines by gel chromatography
nBe generally 1500-8000 gram/mole.
Polyester dispersions or solution D) the number-average molecular weight M that determines by gel chromatography
nBe generally 7500-5000 gram/mole, be preferably 1000-3500 gram/mole.
Coating composition of the present invention is specially adapted to produce anti-stone and hits undercoat.Perhaps, coating composition of the present invention can be used for preparing any required transparent, coloured or Flat paint that is used for single coating or overbrushing layer articles for use.
Coating composition of the present invention is applicable to automobile precision work or soft-feel paint.In these were used, suitable substrates was plastics, timber, metal, mineral substrates, fabric, leather and/or glass.
Coating composition of the present invention also can be used for producing any required transparent, coloured or Flat paint that is used for many articles for use, and these coating are intended to be used for single coating or overbrushing layer articles for use.
Therefore, the present invention also provides a kind of coating system, and this system comprises base material and at least one coating of being made up of water-based paint compositions of the present invention.
If it is suitable, paint and coating by coating composition preparation of the present invention also can comprise tackiness agent, reactive thinner and have the polymkeric substance of unsaturated group that can be by ultraviolet light polymerization, organic and/or mineral dye, carbon black, filler, other solvent, thickening material, rheologic additive, the organic or inorganic nano particle is (for example, based on silicon, zinc, titanium, barium, calcium, magnesium etc.), be used to improve the additive of pigment wettability, the additive that is used for froth breaking, be used for improving and flow, the additive of gloss or adhesion, be used to prevent or reduce the additive of yellowing or UV-light harmful effect.
Can be coated with by spraying, flow coat, dip-coating, roller coat, brushing and cylinder and apply.
Embodiment
Used component:
Raw material A 1) Bayhydrol
A 145:
The water-based hydroxyl official can secondary polyacrylate dispersion.Solids content is that 45%, 23 ℃ viscosity is 1000mPas, and the pH value is 8.0, and acid number is 10 milligrams of KOH/ gram solids, and OH content is 1.5%, contains each butyleneglycol and solvent naphtha 100 of 4%, Bayer MaterialScience AG, Germany.Raw material A 2) Bayhydrol
XP 621:
Water-based aliphatic series no-solvent polyurethane dispersion.Solids content is that 40%, 23 ℃ viscosity is 20 " (DIN4 cup, flowing times); The pH value is 7.5, and mean particle size (the related spectrum of laser) is 100 nanometers, contains carboxylic acid ester groups, Bayer MateriaiScience AG, Germany.
Raw material A 3) Bayhydrol
PT 241:
Water-based hydroxyl functional polyester-polyurethane dispersions.Solids content is 41%, and viscosity is 1000mPas, and the pH value is 8.3, and acid number is 7.5 milligrams of KOH/ gram solids, and OH content is 1%, contains 5% N-Methyl pyrrolidone, Bayer MaterialScience AG, Germany.
Dispersion A):
50 parts of raw material A 1), 15 parts of raw material A 2) and 35 parts of raw material A 3) mixture, above-mentioned umber all is based on the solids content of each raw material.Solids content is 42.7%.
Crosslinking agent B):
Raw material B1) Cymel
328:
Methylated melamine-formaldehyde crosslinking agent resin, the aqueous solution, Cytec Industries Inc., the U.S..
Raw material B2) Cymel
327:
Methylated melamine-formaldehyde crosslinking agent resin, isobutanol solution, Cytec Industries Inc., the U.S..
Raw material C) Bayhydrol
XP 2621:
Water-based aliphatic series no-solvent polyurethane dispersion.Solids content is that 40%, 23 ℃ viscosity is 20 " (DIN4 cup, flowing times); The pH value is 7.5, and mean particle size (the related spectrum of laser) is 100 nanometers, contains carboxylic acid ester groups, Bayer MateriaiScience AG, Germany.
Raw material D) Bayhydrol
D270:
Water-dilutable hydroxyl-functional polyester.Solids content 70%, in water 11.5%, butyleneglycol 13.3%, dimethylethanolamine 5.2%.23 ℃ viscosity is 12000mPas, and the pH value is 8.0, and OH content is 2.0, and acid number is 35 milligrams of KOH/ gram solids, and mean particle size is 15 nanometers, Bayer MaterialScience AG, Germany.
BYK 347: polyether-modified siloxanes, Byk Chemie, Wesel, Germany
Viscalex
HV30,30% supply of material form: (copolymer based thickening material, Allied Colloids LTD, Britain
Disperbyk
190: the segmented copolymer that pigment is stable, Byk Chemie, Wesel, Germany
Byk
011: defoamer; Byk Chemie, Wesel, Germany
Gasru β FW 200 carbon blacks: (Degussa AG, Frankfurt, Germany)
Additol
XL250: pigment wetting additive, Cytec Surface Specialities; The U.S.
Bayhytherm
3146 contain the polyurethane dispersions of blocked isocyanate base, Bayer
MaterialScience AG, Leverkusen, Germany
Maprenal
MF 904 melamine resins: neos Melamins GmbH, Frankfurt, Germany
Maprenal
MF 915 melamine resins: Ineos Melamins GmbH, Frankfurt, Germany
Bayhytherm
VP LS 2153: the polyurethane dispersions of self-crosslinking, Bayer MaterialScience AG;
Leverkusen, Germany
Embodiment 1): the present invention
The preparation and test the anti-stone of single black of the present invention (uni-black) and hit undercoat binder combination 1), this combination 1) binder ingredients is by 48.5% dispersion A), 30% raw material C), 20% raw material B2) and 1.5% raw material D) form, above-mentioned each percentage ratio all is to be benchmark with the solids content.
With 37 parts of dispersion A), 24 parts of raw material C), 7 parts of raw material B2), 4.7 parts of butyleneglycols, 0.5 part of BYK
347,0.9 part of Viscalex
30,12 parts of distilled water of HV and 3.3 parts of dimethylethanolamines (10% aqueous solution form) are introduced as initial charge, mix under the rotating speed of 2000rpm with the dissolver that has propeller type stirrer.Add 10.5 parts of pigment thickeners then, mixture was stirred 30 minutes under the rotating speed of 4000rpm, then the pH value is adjusted to 8.0-8.5.The pigment thickener contains 4.5 parts of raw material D), 14.8 parts of dimethylethanolamines (10% aqueous solution form), 30 parts of Disperbyk
190,0.9 part of Byk
011,17 parts of Gasru β FW 200 and 32 parts of water, and be by disperseing each component in dissolver disperseed 30 minutes in ball mill and preparation then.
The anti-stone of the single black of the water-based of preparation hits base paint 1 like this) pH value be 8-8.5, viscosity is 25 seconds (DIN4 cups, flowing time at 23 ℃), on this coating paint metal sheet, two kinds of different surfacers (Class1 and type 2) have been coated with on this plate, 80 ℃ of dryings 10 minutes, apply the two component polyurethane finish paint then, solidified 30 minutes at 140 ℃.In order to compare, monochrome (uni-colour) base paint with OEM British Standard, Automobile Series quality is carried out identical test.
Table 1: the anti-stone of single black hits undercoat 1)
| Single black basecoat OEM British Standard, Automobile Series quality | The anti-stone of single black hits undercoat (embodiment 1) | |
| On the surfacer of Class1 | ||
| Anti-hitting property of stone (VDA test) * | 1.5 | 1.5 |
| Anti-stone hits the tackiness (1=very good, 2=good, 3=poor) of undercoat to surfacer | 2 | 1-2 |
| The main surface of separation of leafing **DOI *** | Surfacer/electropaining layer 80 | Surfacer/electropaining layer 80-90 |
| On the surfacer of type 2 | ||
| Anti-hitting property of stone (VDA test) * | 2 | 1.5 |
| Anti-stone hits the tackiness (1=very good, 2=good, 3=poor) of undercoat to surfacer | 2 | 1-2 |
| The main surface of separation of leafing **DOI *** | Surfacer/electropaining layer 80 | Surfacer/electropaining layer 80-90 |
*VDA[German Carmakers Association (German automobiles is made association)], the anti-stone of coating hits test: part 1: many Impact Tests, very good according to DIN 55996-1:1=, the non-constant of 5=
*Delamination occurs under serious the exposure: anti-stone hit undercoat with dissimilar surfacers is bonding must be very good, and leafing only occurs over just between surfacer and the electropaining layer (=main surface of separation)
* *The measurement of DOI (image difference) is the gloss measurement near reflection angle, describes the retentivity of finish paint, and this measurement is carried out in the device that is called luminous case (glow box).The value that obtains is relative value (0-100).DOI is high more, and the quality of paint is good more, and the high-contrast article are big more by the difference of the image of the reflection on the surface through painting.Being equal to or greater than 80 value is extraordinary value.
Anti-stone hits undercoat I) meet accurately machined all requirements of automobile.Quality does not rely on the type of base material or surfacer substantially, and the optical property of film and anti-stone hit that character is splendid, the tackiness of the British Standard, Automobile Series quality that tackiness is better than testing as a comparison.
Embodiment 2): the present invention
Preparation and test the anti-stone of single black of the present invention and hit undercoat binder combination 2), this combination 2) binder ingredients by 84% dispersion A), 15% raw material B2) and 1% raw material D) form, above-mentioned each percentage ratio all is to be benchmark with the solids content.
With 60.7 parts of dispersion A, 7.2 parts of linking agent raw material B2), 4.8 parts of butyleneglycols, 0.5 part of BYK
347,1 part of Viscalex
The dimethyl ethanol amine aqueous solution of 30,12 parts of distilled water of HV and 3 part of 10% concentration is in dissolver, under the rotating speed of 2000rpm, stirred 10 minutes, add 10.7 parts of pigment thickeners then, this pigment thickener is by 4.6 parts of raw material D), the dimethyl ethanol amine aqueous solution of 14.9 part of 10% concentration, 30 parts of Disperbyk
190,17 parts of Gasru β FW 200 and 32.42 parts of distilled water are formed, and mixture was stirred 30 minutes under the rotating speed of 4000rpm.
The anti-stone of single black hits undercoat 2) the viscosity that applies be 25 seconds (DIN 4 flow cups/23 ℃), the pH value is about 8, solids content is 30.6%.On this coating paint metal sheet, be coated with the urethane surfacer on this plate, then 80 ℃ of dryings 10 minutes, apply two component polyurethane finish paint commonly used in the automotive industry then, solidified 30 minutes at 140 ℃.
Embodiment 3): the present invention
As embodiment 2), but component ratio is 69.5% dispersion A), 29.4% raw material B2) and 1% raw material D).
The anti-stone of the single black of water-based hits undercoat 3) solids content be 32.5%, with 25 seconds (4 glasss of DIN, flowing time, 23 ℃) viscosity paint metal sheet on, be coated with the urethane surfacer on this plate, 80 ℃ of dryings 10 minutes, apply the two component polyurethane finish paint then, solidified 30 minutes at 140 ℃.
Test result is as follows:
Table 2: the anti-stone of single black hits undercoat 3
| The anti-stone of single black hits undercoat | ||
| Embodiment 2 | Embodiment 3 | |
| Apply viscosity | 25 seconds | 25 seconds |
| Solids content | 30.6％ | 32.5％ |
| DOI (vision) | 80-90 | 80-90 |
| Anti-hitting property of stone (VDA test) | 1.5 | 1.5 |
| Anti-stone hits the tackiness (1=very good, 2=good, 3=poor) of undercoat to surfacer | 1-2 | 1-2 |
| The main surface of separation of leafing ** | Surfacer/electropaining layer | Surfacer/electropaining layer |
Embodiment 4): the present invention
Prepare the anti-stone of silver metal of the present invention and hit undercoat, this coating is by 49 parts of dispersion A), 29 parts of raw material C), 19 parts of raw material B1) and 2 parts of raw material D) form, above-mentioned umber all is to be benchmark with the adhesive solids.
With 17.5 parts of dispersion A), 11.2 parts of raw material C), 19 parts of distilled water, 3.3 parts of butyleneglycols, 4.5 parts of dimethylethanolamines (the aqueous solution) as 10% in dissolver, under the rotating speed of 2000rpm, stirred 10 minutes, add 2.8 parts of Viscalex then
HV30 and 19 parts of distilled water, with mixture again in dissolver, under the rotating speed of 2000rpm, stirred 10 minutes, add 3.5 parts of raw material B1 then), 3.3 parts of butyleneglycols and 4.2 parts of distilled water, in dissolver, continue to stir 10 minutes, add 11.7 parts of metallicity thickeners then, composition was stirred 30 minutes under the rotating speed of 4000rpm.Then, the pH value is adjusted to 8-8.5.
By with 41.9 parts of butyleneglycols, 2.9 parts of raw material D), 4.3 parts of Additol
XL250,50.6 parts of StapaHydrolan
2156 No.55900/G aluminium and 0.23 part of dimethylethanolamine are in dissolver, and stirring prepared the metallicity thickener in 30 minutes under the rotating speed of 4000rpm.
Anti-stone hits undercoat 4) solids content be 18.7%, apply viscosity and be about 40 seconds (DIN 4 flow cups).Can be by spraying with on this coating paint metal sheet, (type a) to be coated with electropaining layer and surfacer on this plate, 80 ℃ of dryings 10 minutes, be coated with 60% two-pack PU Clear paint then, solidified 30 minutes at 140 ℃ based on hydroxyl-functional polyester-polyacrylate and low viscosity HDI Quito isocyanic ester.The thickness of desciccator diaphragm is that undercoat is about 15 microns, and Clear coating is about 40 microns.
Type surfacer a) contains the water-dilutable hydroxyl-functional polyester (Bayhydrol as its binder ingredients
D270), the polyurethane dispersions (Bayhytherm that contains the blocked isocyanate base
3146)) and amino crosslinker resin M aprenal
MF 904 and Marpenal
MF915, ratio is 30: 55: 7.5: 7.5.
Embodiment 5): the present invention
Described according to embodiment 4 by 29 parts of dispersion A), 49 parts of raw material C), 20 parts of raw material B1) and 2 parts of raw material D) preparation silver metal anti-stone hits undercoat.
Anti-stone hits undercoat 5) solids content be 15.9%, apply viscosity and be about 40 seconds (DIN 4 flow cups).Can be by spraying with on this coating paint metal sheet, (type a) to be coated with electropaining layer and surfacer on this plate, 80 ℃ of dryings 10 minutes, be coated with 60% two-pack PU Clear paint then, solidified 30 minutes at 140 ℃ based on hydroxyl-functional polyester-polyacrylate and low viscosity HDI Quito isocyanic ester.The thickness of desciccator diaphragm is that undercoat is about 15 microns, and Clear coating is about 40 microns.
The gained test result is as follows:
Table 3: the anti-stone of silver metal hits undercoat
| The anti-stone of silver metal hits undercoat (on the surfacer of type a) | ||
| Embodiment 4 | Embodiment 5 | |
| Apply viscosity | 40 seconds | 40 seconds |
| Solids content | 18.7% | 15.9% |
| Metallic travel value (X-rite) | ||
| 25 °/75 ° of Δs | 66.5 (107.8/52.1) | 68.3 (108/39.7) |
| 15 °/110 ° of Δs | 95.8 (129.5/33.7) | 103.8 (137.3/33.5) |
| In paint systems, test: | ||
| (the VDA test of anti-hitting property of stone *) | 1-1.5 | 1-1.5 |
| Anti-stone hits undercoat to the tackiness of surfacer (1=very good, 2=is good, 3=is poor) | 1-2 | 1-2 |
| The main surface of separation of leafing * | Surfacer/electropaining layer | Surfacer/electropaining layer |
| *1=is very good, the non-constant of 5= | ||
| * *Under serious the exposure, delamination occurs between surfacer and electropaining layer.Anti-stone hits undercoat and surfacer is very goodly bonding; And the main surface of separation of leafing is surfacer/electropaining aspect. | ||
With different surfacer (type b) repeated experiments 4) and 5), this surfacer is based on Bayhydrol
D270, Bayhytherm
3146, Bayhytherm
(ratio is 20: 32.5: 32.5: 15) for VP LS 2153 and Cymel 327.
The gained test result is as follows:
Table 4: the anti-stone of silver metal hits undercoat
| The anti-stone of silver metal hits undercoat (on the surfacer of type b) | ||
| Embodiment 4 | Embodiment 5 | |
| Apply viscosity | 40 seconds | 40 seconds |
| Solids content | 18.7％ | 15.9％ |
| In paint systems, test: | ||
| (the VDA test of anti-hitting property of stone *) | 1-1.5 | 1 |
| Undercoat is to the tackiness (1=is very good, and 2=is good, and 3=is poor) of surfacer | 1-2 | 1-2 |
| The main surface of separation of leafing ** | Surfacer/electropaining layer | Surfacer/electropaining layer |
| *The grade of 0-5; 1=is very good, the non-constant of 5= | ||
| ***Under serious the exposure, delamination occurs between surfacer and electropaining layer; Anti-stone hits undercoat and surfacer is very goodly bonding | ||
Do not rely on the character of base material, not only shown splendid film optical value and metallic effect but also have splendid anti-hitting property of stone and the anti-stone of adhesion value hits undercoat.All coatings all show the extraordinary tolerance that water is exposed, must, show splendid film optical quality.Corresponding paint formulation is stable when storing.
Binder combination of the present invention is specially adapted to produce anti-stone and hits undercoat, can automobile is accurately machined to be hit four lacquer coating systems that surfacer, undercoat and finish paint form by priming paint, anti-stone and be reduced to by priming paint, anti-stone and hit three coating systems that undercoat and Clear coating are formed with being usually used in.Can obviously reduce accurately machined cost like this.
Though for the purpose of illustrating, the present invention is being described in detail in the preamble, but should understand, these are described in detail only is in order to illustrate that those skilled in the art can make amendment to it under situation without departing from the spirit and scope of the present invention, and the present invention only is defined by the claims.
Claims (15)
1. water-based paint compositions, it comprises by A1), A2) and the aqueous binder mixture A that A3) forms) and B), wherein:
A1) the secondary hydroxyl official of 25 weight % to 70 weight % energy polyacrylate dispersion or polyacrylate dispersion,
A2) the aliphatic urethane dispersion of 5 weight % to 50 weight %,
A3) the hydroxyl-functional polyester-polyurethane ester dispersion of 20 weight % to 70 weight %, molecular weight are that the polyester of 500-2500 gram/mole accounts for 75 weight % at least,
B) at least a linking agent,
Described composition must comprise A1) to A3) in three kinds of components at least two kinds, must the amount of comprising be at least a kind of component A1 of 35 weight %) and/or A3).
2. water-based paint compositions as claimed in claim 1 is characterized in that, its organic solvent content is 2 weight % to 12 weight %.
3. water-based paint compositions as claimed in claim 1 is characterized in that B component) be the amino crosslinker resin.
4. water-based paint compositions as claimed in claim 1 is characterized in that B component) be the combination of amino crosslinker resin and polyisocyanates.
5. water-based paint compositions as claimed in claim 1 is characterized in that it comprises:
C) one or more are selected from polyurethane dispersions C1), polyacrylate dispersion C2) or polyurethane-polyacrylate dispersion C3) dispersion.
6. as claim 1 and 5 described water-based paint compositions, it is characterized in that it comprises:
A) the aqueous binder mixture of 15 weight % to 90 weight %,
B) at least a linking agent of 5 weight % to 40 weight %,
C) one or more of 5 weight % to 65 weight % are selected from polyurethane dispersions C1), polyacrylate dispersion C2) or polyurethane-polyacrylate dispersion C3) dispersion,
A), B) and percentage ratio sum C) be 100 weight %.
7. water-based paint compositions as claimed in claim 1 is characterized in that it comprises:
C) one or more are selected from polyurethane dispersions C1), polyacrylate dispersion C2) or polyurethane-polyacrylate dispersion C3) dispersion,
D) water-dilutable hydroxyl-functional vibrin.
8. as claim 1 and 7 described water-based paint compositions, it is characterized in that it comprises:
A) the aqueous binder mixture of 15 weight % to 89.5 weight %,
B) at least a linking agent of 5 weight % to 40 weight %,
C) one or more of 5 weight % to 65 weight % are selected from polyurethane dispersions C1), polyacrylate dispersion C2) or polyurethane-polyacrylate dispersion C3) dispersion,
D) the water-dilutable hydroxyl-functional vibrin of 0.5 weight % to 30 weight %,
A), C B)) and percentage ratio sum D) be 100 weight %.
9. water-based paint compositions as claimed in claim 5 is characterized in that component C) be the dispersion of physical dryness.
10. water-based paint compositions as claimed in claim 1 is characterized in that it comprises:
D) water-dilutable hydroxyl-functional vibrin.
11., it is characterized in that it comprises as claim 1 and 10 described water-based paint compositions:
A) the aqueous binder mixture of 30 weight % to 94.5 weight %,
B) at least a linking agent of 5 weight % to 40 weight %,
D) the water-dilutable hydroxyl-functional vibrin of 0.5 weight % to 30 weight %,
A), B) and percentage ratio sum D) be 100 weight %.
12. water-based paint compositions as claimed in claim 7, it is characterized in that, component D) acid number is a 25-75 milligram KOH/ gram solid, and/or hydroxy radical content is 2.5 weight % to 10 weight %, and/or molecular weight is 750-5000 gram/mole, and/or the content of fatty acid component is 15 weight % to 50 weight %.
13. anti-stone hits base paint, it comprises water-based paint compositions as claimed in claim 1.
14. paint systems, it comprises base material and at least one coating of being made up of water-based paint compositions as claimed in claim 1.
15. base material as claimed in claim 14 is characterized in that, described base material is selected from plastics, timber, metal, mineral substrates, fabric, leather, glass and their combination.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006048926A DE102006048926A1 (en) | 2006-10-17 | 2006-10-17 | Aqueous coating agent based on a binder mixture as a basecoat |
| DE102006048926.8 | 2006-10-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101173146A true CN101173146A (en) | 2008-05-07 |
Family
ID=38826506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101803572A Pending CN101173146A (en) | 2006-10-17 | 2007-10-16 | Aqueous coating composition based on a binder mixture as a base coat |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US8383724B2 (en) |
| EP (1) | EP1914282B1 (en) |
| JP (1) | JP2008115385A (en) |
| KR (1) | KR20080034788A (en) |
| CN (1) | CN101173146A (en) |
| AT (1) | ATE443741T1 (en) |
| BR (1) | BRPI0703892A (en) |
| CA (1) | CA2606562A1 (en) |
| DE (2) | DE102006048926A1 (en) |
| ES (1) | ES2331159T3 (en) |
| MX (1) | MX2007012824A (en) |
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- 2006-10-17 DE DE102006048926A patent/DE102006048926A1/en not_active Withdrawn
-
2007
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- 2007-10-04 ES ES07019442T patent/ES2331159T3/en active Active
- 2007-10-04 DE DE502007001570T patent/DE502007001570D1/en active Active
- 2007-10-04 AT AT07019442T patent/ATE443741T1/en active
- 2007-10-12 CA CA002606562A patent/CA2606562A1/en not_active Abandoned
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- 2007-10-16 CN CNA2007101803572A patent/CN101173146A/en active Pending
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| CN108373839A (en) * | 2016-10-11 | 2018-08-07 | 株式会社Kcc | water-soluble coating composition |
| CN107880705A (en) * | 2016-11-22 | 2018-04-06 | 南亚塑胶工业股份有限公司 | Water-based environment-friendly coating with high hardness and high adhesion characteristics and preparation method thereof |
| US10626286B2 (en) | 2016-11-22 | 2020-04-21 | Nan Ya Plastics Corporation | Low-VOC-emission waterborne coating having high hardness and good adhesion and process for producing the same |
| CN111320928A (en) * | 2020-03-23 | 2020-06-23 | 山东七维新材料有限公司 | High-gloss high-DOI waterborne polyurethane coating and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20080090957A1 (en) | 2008-04-17 |
| MX2007012824A (en) | 2008-10-28 |
| CA2606562A1 (en) | 2008-04-17 |
| BRPI0703892A (en) | 2008-06-03 |
| DE502007001570D1 (en) | 2009-11-05 |
| JP2008115385A (en) | 2008-05-22 |
| EP1914282B1 (en) | 2009-09-23 |
| EP1914282A1 (en) | 2008-04-23 |
| KR20080034788A (en) | 2008-04-22 |
| US8383724B2 (en) | 2013-02-26 |
| ATE443741T1 (en) | 2009-10-15 |
| DE102006048926A1 (en) | 2008-04-24 |
| ES2331159T3 (en) | 2009-12-22 |
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